U.S. patent number 7,659,354 [Application Number 10/540,198] was granted by the patent office on 2010-02-09 for hydrophobically modified polymers as laundry additives.
This patent grant is currently assigned to Ciba Specialty Chemiclas Corporation. Invention is credited to Jianwen Mao, Ullrich Menge, Hauke Rohwer, Zhiqiang Song.
United States Patent |
7,659,354 |
Song , et al. |
February 9, 2010 |
**Please see images for:
( Certificate of Correction ) ** |
Hydrophobically modified polymers as laundry additives
Abstract
The present invention is directed to polymeric compounds
comprising a main backbone derived from at least the following
monomeric components: (I) 20 to 99.9% by weight, preferably 50% to
99% by weight, of at least one cationic monomer according to
formula (I), and (II) 0.1 to 80% by weight of a hydrophobic
unsaturated nonionic monomer that polymerizes in the presence of an
initiator, optionally a water-soluble monomer (III) different from
either monomer (I) and monomer (II), and optionally a crosslinking
agent (IV). Said compounds are particularly useful to overcome the
problem of dye bleeding and/or dye transfer in laundry processes.
##STR00001##
Inventors: |
Song; Zhiqiang (Newtown,
CT), Mao; Jianwen (New Milford, CT), Rohwer; Hauke
(Lorrach, DE), Menge; Ullrich (Grenzach-Wyhlen,
DE) |
Assignee: |
Ciba Specialty Chemiclas
Corporation (Tarrytown, NY)
|
Family
ID: |
32685430 |
Appl.
No.: |
10/540,198 |
Filed: |
December 15, 2003 |
PCT
Filed: |
December 15, 2003 |
PCT No.: |
PCT/EP03/51000 |
371(c)(1),(2),(4) Date: |
August 08, 2006 |
PCT
Pub. No.: |
WO2004/056888 |
PCT
Pub. Date: |
July 08, 2004 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20060287216 A1 |
Dec 21, 2006 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60509032 |
Oct 6, 2003 |
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60436040 |
Dec 23, 2002 |
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Current U.S.
Class: |
526/307; 8/137;
525/328.3; 510/499; 510/475; 510/361; 510/477 |
Current CPC
Class: |
C11D
3/3773 (20130101); C08F 226/04 (20130101); D06P
5/08 (20130101); C11D 3/0021 (20130101); C11D
3/3769 (20130101); D06P 1/5257 (20130101); D06P
1/5242 (20130101); C08F 226/04 (20130101); C08F
220/14 (20130101); C08F 226/04 (20130101); C08F
220/306 (20200201); C08F 226/04 (20130101); C08F
220/1804 (20200201); C08F 226/04 (20130101); C08F
220/30 (20130101); C08F 226/04 (20130101); C08F
220/306 (20200201) |
Current International
Class: |
C08F
226/04 (20060101); C08F 220/14 (20060101); D06P
5/08 (20060101); C11D 3/37 (20060101); C08F
220/18 (20060101); C08F 220/30 (20060101) |
Field of
Search: |
;510/361,475,477,499
;8/137 ;525/328.3 ;526/307 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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296307 |
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Nov 1991 |
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DE |
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0232519 |
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Aug 1987 |
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EP |
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0685591 |
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Dec 1995 |
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EP |
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0995791 |
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Apr 2000 |
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EP |
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1372787 |
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Nov 1974 |
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GB |
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97/42285 |
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Nov 1997 |
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WO |
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98/23714 |
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Jun 1998 |
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WO |
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01/79407 |
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Oct 2001 |
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WO |
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02/20709 |
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Mar 2002 |
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WO |
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Primary Examiner: Mruk; Brian P
Attorney, Agent or Firm: Suhadolnik; Joseph Mansfield; Kevin
T
Parent Case Text
This application is a 371 filing of EP 03/51000 which claims
benefit under 35 USC 119(e) of U.S. provisional application No.
60/509,032 filed Oct. 6, 2003 and 60/436,040, filed Dec. 23, 2002,
the disclosures of which are incorporated herein in their entirety
by reference.
Claims
We claim:
1. A polymeric compound formed from a mixture of monomeric
components consisting of: (I) 20 to 99.9% by weight of at least one
cationic monomer according to formula (1) ##STR00012## where
R.sub.1 and R.sub.2 are, independently of one another, hydrogen or
C.sub.1-C.sub.4 alkyl; R.sub.3 and R.sub.4 are, independently of
one another, hydrogen, or an alkyl, hydroxyalkyl, carboxyalkyl,
carboxyamidealkyl or alkoxyalkyl group having from 1 to 18 carbon
atoms; and Y.sup.- represents an anion; (II) 0.1 to 80% by weight
of at least one hydrophobic unsaturated nonionic monomer that
polymerizes in the presence of an initiator selected from the group
consisting of styrene, esters of (meth)acrylic acid,
(meth)acrylonitrile, esters of unsaturated polyfunctional acids and
vinyl esters of C.sub.2 to C.sub.18 carboxylic acids; (III) 0 to
60% by weight of a water-soluble monomer different from monomer (I)
and monomer (II) selected from the group consisting of vinyl amine,
vinyl alcohol, vinyl derivatives of dimethyl siloxane,
aminosiloxanes, hydroxyalkyl acrylates, (meth)acrylic acid and
(meth)acrylic acid salts; and (IV) 0 to 10% by weight a
crosslinking agent.
2. A polymeric compound according to claim 1 wherein at least one
cationic monomer (I) is selected from the group consisting of
diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl
ammonium bromide, diallyldimethyl ammonium sulfates,
diallyldimethyl ammonium phosphates, dimethallyl dimethyl ammonium
chloride, diethylallyl dimethyl ammonium chloride, diallyl
di(beta-hydroxyethyl) ammonium chloride, and diallyl
di(beta-ethoxyethyl) ammonium chloride.
3. A polymeric compound according to claim 1 wherein at least one
cationic monomer (I) is diallyldimethyl ammonium chloride
(DADMAC).
4. A polymeric compound according to claim 1 wherein hydrophobic
monomeric reactant (II) has a value for water solubility of less
than about 50 g/100 g of water at room temperature and a pH of
7.
5. A polymeric compound according to claim 1 wherein at least one
hydrophobic monomer (II) is represented by formula (B) ##STR00013##
where R.sub.5 is H or CH.sub.3, and R.sub.6 is C.sub.1-C.sub.12
alkyl, C.sub.1-C.sub.6 alkylphenyl that may be substituted one to
three times by C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 alkoxy,
or C.sub.1-C.sub.6 alkylphenyl interrupted one or more times by
oxygen wherein the phenyl group may be substituted one to three
times by C.sub.1-C.sub.12 alkyl or C.sub.1-C.sub.12 alkoxy;
C.sub.1-C.sub.6alkylhydroxy and X is a divalent oxygen radical.
6. A polymeric compound according to claim 1 wherein hydrophobic
monomer (II) is selected from the group consisting of ##STR00014##
wherein R.sub.5 is H or CH.sub.3.
7. A polymeric compound according to claim 1 wherein water-soluble
monomer (III) has a value for water solubility greater than 50
g/100 g water at room temperature and at a pH of 7.
8. A polymeric compound according to claim 1 having an average
molecular weight in the range of 1000 to 5 million Daltons.
9. A cleaning product comprising the polymeric compound according
to claim 1 and an effective amount of one or more surfactants.
10. A cleaning product according to claim 9 in the form of a
laundry detergent, fabric conditioner, pre-treatment agent, after
treatment agent or tumble dry sheet having improved dye fixation
and dye transfer inhibition.
11. A cleaning product according to claim 9 in the form of a
dishwashing formulation.
12. A cleaning product according to claim 9 comprising 0.001% to
50% by weight of said polymeric compound.
13. A cleaning product according to claim 9 further comprising at
least one modifying ingredient selected from the group consisting
of softeners, perfumes, soil release polymers, colorants,
preservatives, antimicrobials, insect repellents, dust mites
repellents, optical brighteners, UV absorbers, other light
management agents, ionization agents, antifoam agents, enzymes,
bleaching agents, oxidation catalysts, zeolites, and odor
suppressing agents.
14. A textile processing formulation comprising 0.001% to 50% by
weight of a polymeric compound according to claim 1 in liquid or
solid form.
15. Dyeing or printing auxiliaries and/or finishing agents
comprising the textile formulation according to claim 14.
16. A method for textile processing comprising addition of the
textile formulation according to claim 14 before, during and after
dyeing to improve the wet fastness and prevent color fading of the
textile.
Description
BACKGROUND
Various attempts have been made to overcome the problem of dye
bleeding and/or dye transfer in laundry processes. The term "dye
bleeding" often refers to the fact that certain dyes will come off
the fabrics during laundering, thereby causing color fading of the
fabrics. Such a phenomenon seems to be more prominent for
cellulosic fabrics dyed with non-reactive dyes such as direct, vat,
azoic and sulfur dyes (D R. Warring and G. Hallas, "The chemistry
and application of dyes", Plenum Press, New York, 1990). Dyes that
come off the fabrics are often called "migrating dyes" and the
process to overcome dye bleeding are often referred to as "dye
fixation".
On the other hand, there is also a need to take care of the
migrating dyes that have already come off the fabrics and are
present in the wash liquor. Otherwise, such migrating dyes might
redeposit on fabric surfaces and thereby cause color contamination.
This process is often referred to as "dye transfer inhibition"
and/or "stain inhibition".
Hence there is a need for additives that can be added into laundry
detergents and/or after rinse products to help either prevent dyes
on fabrics from bleeding, i.e. fixing, or substances that can
prevent migrating dyes from re-deposition. Indeed much efforts have
been made to overcome such problems, and substances that could help
tackle such problems are often referred as dye fixatives, dye
transfer inhibitors, anti-deposition agents, dye scavengers and/or
staining inhibitors.
For example, U.S. Pat. No. 3,694,364, there is disclosed the use of
tertiary polymeric amines which function as anionic dye scavengers.
The polymeric amines are chemically affixed on the surface of a
substrate material such as cellulosic materials, for example,
cotton in any of its forms, purified cotton cellulose, cellulose
sponge and the like. To affix the polymeric amines, the cotton
substrate is modified by phosphorylation and chemisorption of the
polymeric amine. In related U.S. Pat. No. 3,673,110, there is
disclosed the use of both the tertiary polymeric amines and
quaternary ammonium compounds as the dye scavenging material. The
latter Edwards patent discloses other processes for chemically
affixing the dye scavenger compounds to a cellulosic material
substrate also for use in controlling undesirable random dyes in a
liquid bath such as when laundering textile articles. For example,
the hydroxylated surface of the cellulosic material is chemically
modified to establish anionic functional groups. Each of the
anionic functional groups is capable of chemically binding nitrogen
compounds such as the aforementioned disclosed dye scavenger
compounds.
In addition to modifying the fabric surface to present dye
transfer, it is also possible to add into the laundry sacrificial
materials that absorb migrating dyes, thereby prevent the
re-deposition on fabrics of value and concern. Such materials are
often made in the form of fabrics treated with various chemicals
that are believed to be capable to attracting dyes from the wash
liquor. In Kleinschmidt, U.S. Pat. No.3,816,321 there is disclosed
a dye scavenging article for scavenging anionic dyes released from
dyed fabrics being laundered to prevent dye transfer during the
laundry process. The dye-scavenging article includes a support
matrix such as a polyurethane material to which there is chemically
bonded a dye-scavenging compound. The dye-scavenging compound
includes polyquartenary ammonium compounds.
U.S. Pat. No. 4,380,453 discloses generally the use of
N-trisubstituted ammonium-2-hydroxy-3-halopropyl compounds and
salts of epoxy propyl ammonium as dye scavenger compounds. The
preferred dye scavenger compound is glycidyltrimethylammonium
chloride, which is applied to, adsorbed by, or impregnated in the
cellulosic material substrate. The resulting cellulosic material
substrate is disclosed as being suitable for use in conventional
washing machines for laundering clothes to eliminate random dyes
from the wash and rinse waters, thereby eliminating undesirable
discoloration of clothes due to the transfer of dyes from other
clothes in the washing machine.
U.S. Pat. No. 5,698,476 discloses an article for removing
extraneous, random free-flowing dyes from laundry washing
applications. The laundry article includes two components, a dye
absorber and a dye transfer inhibitor, which are introduced into
the wash water via a support matrix. The dye absorber is chemically
attached to the support matrix to maintain a relational association
during the laundry washing application. On the other hand, the dye
transfer inhibitor is released from the support matrix into the
wash water to be evenly distributed during the laundry washing
application.
U.S. Pat. No. 5,698,476 discloses materials that are suitable as
dye absorbers for the laundry article, including quaternary
N-substituted ammonium)-hydroxy-haloalkyl compounds such as
2-hydroxy-3-chloropropoyltrimethylammonium chloride; polyquaternary
ammonium compounds; polyamphoterics; quaternized starches;
proteins; chitin or its hydrolyzed form, chitosan; choline
chloride; polyvinyl amine (PVAm); polyethylene imine (PEI); as well
as combinations thereof. Dye transfer inhibitors include polyvinyl
pyrrolidone, polyvinyl alcohol, polyvinyl Imidazole,
polyamine-N-oxides, cationic starches, magnesium aluminate,
hydrotalcite, proteins, hydrolyzed proteins, polyethylene imines,
polyvinyl oxazolidone, enzymes, oxidants, cationic surfactants,
amphoteric surfactants, propylene oxide reaction products,
polyamino acids, block co-polymers of alkylene oxides, polyamines,
polyamides, methyl cellulose, carboxyalkyl, celluloses, guar gum,
natural gums, alginic acid, polycarboxylic acids, cydodextrins and
mixtures.
Another approach for tackling the problem of undesirable dye
transfer is through the use of an oxidation catalyst that is
capable of removing migrating dyes in the wash liquor, thereby
preventing re-deposition. Such catalysts, e.g. selected manganese
complexes, can be added into laundry detergents as special
additives.
Certain polymers have also been found to be useful in preventing
migrating dyes from re-deposition. For examples, the use of
poly(vinyl pyridine) and its various derivatives and co-polymers in
preventing dye re-depositions can be found in the following
references.
U.S. Pat. No. 6,348,441 discloses a method for laundering soiled
fabrics using a non-aqueous detergent formulated to control dye
transfer and sudsing in high efficiency washing machine. U.S. Pat.
No. 5,466,802 discloses the use of quaternary polyvinylpyrridinium
derivatives as anti-dye transfer agent. U.S. Pat. No. 6,306,815
discloses the use of quaternary polyvinylpyrridinium derivatives as
anti-dye transfer agents. U.S. Pat. No. 5,380,447 discloses a
process and fabric finishing compositions for preventing the
deposition of dye in fabric finishing processes. U.S. Pat. No.
6,191,098 discloses polyvinylpyridinium derivatives as anti-dye
transfer agents. U.S. Pat. No. 6,156,829 discloses a product and
process for making quaternized, water-soluble vinylpyridine
carboxylate polymers. U.S. Pat. No. 6,271,386 discloses a product
and process for making quaternized, water-soluble vinylpyridine
carboxylate polymers. U.S. Pat. No. 6,103,831 discloses
water-soluble dye complexing polymers. U.S. Pat. No. 5,863,879
discloses dye transfer inhibitors for detergents (BASF, vinylamine
derivatives). U.S. Pat. No. 6,165,969 discloses the use of
quaternized polymerizates containing units of vinyl imidazole as a
color fixing and color transfer inhibiting additive to detergent
post-treatment agents and detergents. U.S. Pat. No. 5,830,844
discloses dye transfer inhibitors for detergents: Water-insoluble
particles, crosslinked polymers containing polymerized units of
1-vinylpyrrolidone and/or 1-vinylimidazoles).
Various derivatives based on vinylpyridinum,
poly(vinylpyridine-N-oxide) have been found to be efficient dye
transfer inhibitors. The preparation and application of such
compounds have been documented in U.S. Pat. No. 6,121,223 and U.S.
Pat. No. 5,149,456.
Amine based products are believed to be able to provide dye
transfer inhibition properties. For example, the use of
N,N,N',N'-tetrakis-(2-hydroxypropyl) ethylenediamine) as dye
transfer inhibitors is explored in U.S. Pat. No. 5,827,813. Other
references relating to the use of amine based substances as dye
transfer inhibitors include U.S. Pat. No. 6,251,846, U.S. Pat. No.
6,156,722 and U.S. Pat. No. 6,140,292.
In addition to the aforementioned references, the use of
polyglycosides (U.S. Pat. No. 6,159,921) and various enzymes
exhibiting peroxidase activities (U.S. Pat. No. 5,855,621) as dye
transfer inhibitors is referred.
In comparison to the seemingly plentiful references on various
substances and their utilities as laundry detergents to provide dye
transfer inhibition properties, there appears to be very few
references on substances that could help prevent bleeding of dyes
from fabrics. Among the very few citations, the use of
bis-(hydroxyphenyl)sulfone with formaldehyde as dye bleeding
prevention agent is reported in U.S. Pat. No. 5,707,949.
The use of nitrogen-containing polymers is known for use in laundry
applications, particularly for soil-release properties. Published
PCT application WO-A-98/23714 discloses water-soluble use of
nitrogen-containing soil-release polymers in detergent products.
Some of these polymers are formed from acrylamide monomers and are
polymerized with co-monomers that are amines of alkylacrylates. A
nitrogen-containing soil release polymer is described in
WO-A-98/23714 and is formed from dicarboxylic add monomers and
hydrophilic co-monomers that are secondary amines, which contain
(poly)alkyleneoxy groups. Published PCT application WO-A-98/23714
discloses polymers formed from alkyleneacrylate monomers having a
terminal quaternary ammonium group and co-monomers, which are
(meth)acrylic add or esters or salts thereof. The only example is a
polymer formed from a cationic monomer, namely methacrylamidopropyl
trimethylammonium chloride (MAPTAC), and anionic monomer, namely
acrylic acid (AA) and a neutral monomer, namely isobutylacrylate
(IsoBuA).
U.S. Pat. No. 3,749,682 discloses copolymers of
polyvinylpyrrolidone (PVP) and vinyl acetate for use as soil
anti-redeposition agents.
Published PCT application WO-97/42285 discloses cotton soil-release
polymers comprising a polyamine backbone and quaternary ammonium
cationic groups.
Published European patent application 995,791 discloses a broad
range of hydrophobically modified polycarboxylate polymers that are
said to be useful for promoting soil release from fabrics,
particularly cotton and cotton-containing fabrics. The polymers can
comprise up to three moieties A, B and C wherein A is a polymerized
residue of a monomer selected from one or more C.sub.3-C.sub.8
monoethylenically unsaturated carboxylic acids, B is a polymerized
residue of a monomer selected from one or more C.sub.3-C.sub.60
alkyl (meth)acrylates, ethoxylated C.sub.1-C.sub.24 alkyl
(meth)acrylates, and poly(alkylene glycol) (meth)acrylates, alkyl
or aromatic ethers of poly(alkylene glycol) and the corresponding
maleate mono and di-esters thereof, and C is a polymerized residue
of a monomer selected from one or more ethylenically unsaturated
monomers which are copolymerizable with the monomers in A and
B.
According to published British patent application 2,104,091,
copolymers of anionic and cationlc vinyl monomers can be used as
detergency builders, for a wide range of detergent products, e.g.
for ware washing, hard surface cleaning, textile cleaning and hair
products.
U.S. Pat. No. 5,783,533 discloses various amphoteric copolymers as
rheological modifiers of lamellar phases of detergent or cosmetic
compositions.
JP-A-59135293 discloses detergent compositions, which contain an
amphoteric copolymer consisting of at least 10 mol % cationic vinyl
monomer units, at least 10 mol % anionic vinyl monomer units and at
least 10 mol % nonionic vinyl monomer units. The preferred
proportion of cationic vinyl monomer units to anionic vinyl monomer
units is a molar ratio from 1:2 to 2:1.
U.S. Pat. No. 5,413,731 disposes water-soluble terpolymers, which
are useful in automatic machine dishwashing detergent formulations.
These terpolymers contain as polymerized units (a) from about 92 to
about 30% by weight of one or more C.sub.3-C.sub.6
monoethylenically unsaturated carboxylic acids, (b) from about 5 to
about 50% by weight of one or more aminoacryloyl derivatives, and
(c) from about 25% by weight of one or more monoethylenically
unsaturated monomers polymerizable with (a) and (b).
OBJECT OF THE INVENTION
One objective is to provide hydrophobically modified polymers that
contain cationic groups, particularly DADMAC moieties and method(s)
for the preparation thereof. Another objective is to provide
methods of use of such polymers as laundry additives that inhibit
the transfer of dyes or fix dyes on fabric surfaces to prevent
bleeding. Polymers having both hydrophobic and cationic groups are
believed to be able to enhance the substantivity of the polymer to
the substrates thereby improving the efficiency of dye fixation
where it is most needed. At the same time these polymers possess
reasonable water solubility/dispersibility that can facilitate the
complexing of the polymers with dyes already lost to the wash
liquor (migrating dyes) thus preventing transfer of the dyes to
other fabrics in the same laundry.
Another objective is to provide methods of applications of such
polymers in formulations that are used to treat surfaces at home or
otherwise indoor environment to prevent staining. Examples of such
surfaces include dishes in dishwashing applications, carpets, wood,
laminate or other types of floors made of organic and inorganic
materials.
Yet another objective of the invention is to provide formulations
of various laundry care products containing the polymers having
both cationic and hydrophobic groups as additives. Such products
include but not limited to laundry detergents, after rinse
conditioners, pretreatment agents, tumble drier sheet,
after-washing sprays etc. It is conceivable that such products
could be in the form of liquid, granules, tablets, or any
combinations thereof. The preparation of such formulations can be
carried out using various processes, machineries known to those who
are skilled in the art. It would also be obvious to those who are
skilled in the art that such products could be packaged in various
forms with various packaging materials.
Another objective of the invention is to provide means of preparing
various forms of laundry care products as aforementioned, but the
performance of such products could be further enhanced by
incorporation of other additives such as softeners, perfumes, soil
release polymers, colorants, preservatives, antimicrobials with
various activities against various microorganisms, insect
repellents, dust mites repellents and/or otherwise controlling
agents, optical brighteners, UV absorbers, other light management
agents, ionization agents, antifoam agents, enzymes of various
kind, bleaching agents, oxidation catalysts, zeolites, odor
suppressing agents including but not limited to cyclodextrin and
its various derivatives. It is obvious to those who are skilled in
the art that other additives and/or agents can also be incorporated
into laundry care products of any forms. An excellent description
of typical laundry detergents and other laundry care products can
be found in, though not limited to, U.S. Pat. No. 5,744,435, the
content of which is incorporated herein by reference.
SUMMARY OF THE INVENTION
The present invention is directed to polymeric compounds comprising
a main backbone derived from at least the following monomeric
components: (I) 20 to 99.9% by weight, preferably 50% to 99% by
weight, of at least one cationic monomer according to formula
(1)
##STR00002## and (II) 0.1 to 80% by weight of a hydrophobic
unsaturated nonionic monomer that polymerizes in the presence of an
initiator; optionally up to 60% by weight of a water-soluble
monomer (III) different from either monomer (I) and monomer (II);
and optionally (IV), a crosslinking agent, in an amount between 0
to 10% by weight.
The subject matter, polymers having both hydrophobic and cationic
groups, described herein are believed to have utilities in addition
to laundry care. Examples could include retention and fixation
agents for paper, wet fastness improvement before, during and/or
after dyeing of fabrics, especially those made of cellulosic
fibers, personal care and cosmetic products such as shampoos,
conditioners, hair colorants, hair styling products, skin cleansing
products, skin care products such as creams, lotions and toners.
Application of the subject materials and various formulations
containing such materials will be disclosed in a separate patent
filing.
The subject matter, polymers having both hydrophobic and cationic
groups, described herein are also believed to be capable of
providing additional effects when used in laundry care
applications. Possible benefits may include, but are not limited
to, Improved hand, e.g. softening, and reduction of friction
between the surfaces of the fabrics. The latter properties are
believed to be capable of leading to consumer-appreciable claims
such as, though not limited to, improved fabric appearance, wear
reduction etc.
DETAILED DESCRIPTION OF THE INVENTION
The polymer having both hydrophobic and cationic groups is
produced, in the presence of an activator, from a polymerization
mixture comprising (I) 20 to 99.9% by weight, preferably 50% to 99%
by weight, of at least one cationic monomer according to formula
(1)
##STR00003## where R.sub.1 and R.sub.2 are, independently of one
another, hydrogen or C.sub.1-C.sub.4 alkyl; R.sub.3 and R.sub.4
are, independently of one another, hydrogen, or an alkyl,
hydroxyalkyl, carboxyalkyl, carboxyamidealkyl or alkoxyalkyl group
having from 1 to 18 carbon atoms; and Y.sup.- represents an anion;
and (II) 0.1 to 80% by weight of a hydrophobic unsaturated nonionic
monomer that polymerizes in the presence of an initiator
The hydrophobic monomeric monomer (II) has a value for water
solubility, preferably, of less than about 50 g/100 g water, and
more preferably, less than 5 g/100 g water at room temperature and
at a pH of 7.
Examples of the preferred cationic monomers (I) include
diallyldimethyl ammonium chloride (DADMAC), diallyldimethyl
ammonium bromide, diallyidimethyl ammonium sulfate, diallyldimethyl
ammonium phosphates, dimethallyldimethyl ammonium chloride,
diethylallyl dimethyl ammonium chloride, diallyl
di(beta-hydroxyethyl) ammonium chloride, and diallyl
di(beta-ethoxyethyl) ammonium chloride. The most preferred cationic
monomer is DADMAC.
Examples of hydrophobic monomer (II) include, without limitation,
selected vinyl and (meth)acrylate based compounds, and other
unsaturated compounds such as (meth)acrylonitrile and esters of
unsaturated polyfunctional acids.
Examples of suitable vinyl compounds for monomer (II) include, but
are not limited to, styrene; vinyl esters of a C.sub.2 to C.sub.18
carboxylic acid, such as vinyl acetate and vinyl butyrate; N-vinyl
amides of a C.sub.2 to C.sub.18 carboxylic acid such as N-vinyl
acetamide, and the like.
The (meth)acrylate based compounds suitable as monomer (II)
include, but are not limited to, esters of (meth)acrylic acid, and
amides of (meth)acrylic acid.
Esters of (meth)acrylic acid or (meth)acrylates encompass: long-
and short-chain alkyl (meth)acrylates such as methyl
(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
isopropyl (meth)acrylate, butyl (meth)acrylate, amyl
(meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,
pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl
(meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate,
isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl
(meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate,
undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl
(meth)acryiate, octadecyl (meth)acrylate, and stearyl
(meth)acrylate; alkoxyalkyl (meth)acrylates, particularly
C.sub.1-C.sub.4alkoxy C.sub.1-C.sub.4alkyl (meth)acrylates, such as
butoxyethyl acrylate and ethoxyethoxyethyl acrylate; aryloxyalkyl
(meth)acrylate, particularly aryloxy C.sub.1-C.sub.4alkyl
(meth)acrylates, such as phenoxyethyl acrylate (e.g., Ageflex, Ciba
Specialty Chemicals) single and multi-ring cyclic aromatic or
non-aromatic acrylates such as cydohexyl acrylate, benzyl acrylate,
dicyclopentadiene acrylate, dicyclopentanyl acrylate,
tricyclodecanyl acrylate, bornyl acrylate, isobornyl acrylate
(e.g., Ageflex IBOA, Ciba Specialty Chemicals), tetrahydrofurfuryl
acrylate (e.g., SR285, Sartomer Company, Inc.), caprolactone
acrylate (e.g., SR495, Sartomer Company, Inc.), and
acryloylmorpholine; alcohol-based (meth)acrylates such as
polyethylene glycol monoacrylate, polypropylene glycol
monoacrylate, methoxyethylene glycol acrylate, methoxypolypropylene
glycol acrylate, methoxypolyethylene glycol acrylate,
ethoxydiethylene glycol acrylate, and various alkoxylated
alkylphenol acrylates such as ethoxylated(4) nonylphenol acrylate
(e.g., Photomer 4003, Henkel Corp.); amides of (meth)acrylic acid
such as diacetone acrylamide, isobutoxymethyl acrylamide, and
t-octyl acrylamide; and esters of polyfunctional unsaturated adds,
such as maleic add ester and fumaric acid ester.
With respect to the long and short chain alkyl acrylates listed
above, a short chain alkyl acrylate is an alkyl group with 6 or
less carbons and a long chain alkyl acrylate is alkyl group with 7
or more carbons. Most suitable monomers are either commercially
available or readily synthesized using reaction schemes known in
the art. For example, most of the above-listed monomers can be
synthesized by reacting an appropriate alcohol or amide with an
acrylic acid or acryloyl chloride.
Specific examples of preferred compounds for use as monomer (II)
are exemplified by:
##STR00004## wherein R.sub.5 is H or CH.sub.3, R.sub.6 is
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy,
C.sub.1-C.sub.6alkylphenyl that may be substituted one to three
times by C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkoxy, or
C.sub.1-C.sub.6alkylphenyl interrupted one or more times by oxygen
wherein the phenyl group may be substituted one to three times by
C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkoxy or
C.sub.1-C.sub.6alkylhydroxy; and X is a divalent radical of --O--,
--NH-- or --NR.sub.7, wherein R.sub.7 is C.sub.1-C.sub.6alkyl.
Preferred compounds are of the formulae:
##STR00005## wherein R.sub.5 and X are defined above and n is a
number from 1 to 5, preferably 2 or 3.
Particularly preferred compounds are of the formulae:
##STR00006## wherein R.sub.5 is H or CH.sub.3.
The polymerization mixture optionally further includes a
water-soluble monomer (III) that is a polymerizable monomer
different from monomer (I) and monomer (II). Water-soluble monomer
(III) has a value for water solubility preferably greater than 50
g/100 g water at room temperature and at a pH of 7.
Water-soluble monomer (III) can be nonionic, anionic or cationic.
Examples of monomer (III) include vinyl amine, vinyl formamide,
vinyl alcohol, vinylpyrrolidone, vinyl caprolactam, vinyl
derivatives of dimethyl siloxane, aminosiloxanes and other
derivatives, various vinyl fluorocarbons, hydroxyalkyl acrylates
such as 2-hydroxyethyl-acrylate, 2-hydroxypropyl-acrylate, and
2-hydroxybutyl-acrylate; aminoalkyl (meth)acrylates such as
dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
diethylaminoethyl acrylate, diethylaminoethyl methacrylate and
7-amino-3,7-dimethyloctyl acrylate, and their salts including their
alkyl and benzyl quaternized salts; (meth)acrylic acid and their
salts; acrylamide, methacrylamide, and N,N-dialkyl acrylamides such
as N,N-dimethyl acrylamide, N,N-diethyl acrylamide, and
N,N'-dimethylaminopropyl acrylamide and their salts. Though
optional, the content of the monomer (III) can be between 0 to 60%
(by weight), preferably between 0 to 20% of the weight of the total
monomers.
The polymerization mixture further optionally contains monomer
(IV), in an amount between 0 to 10% by weight, which is a
crosslinking agent(s). Preferred examples of suitable crosslinking
agents include methylene bisacrylamide, pentaerythritol, di-, tri-
and tetra-acrylate, divenylbenzene, polyethylene glycol diacrylate
and bisphenol A diacrylate.
More generally, suitable crosslinking agents can be polyfunctional
ethylenically unsaturated monomers which include, without
limitation, alkoxylated bisphenol A diacrylates such as ethoxylated
bisphenol A diacrylate with ethoxylation being 2 or greater,
preferably ranging from 2 to about 30 (e.g. SR349 and SR601
available from Sartomer Company, inc. West Chester, Pa. and
Photomer 4025 and Photomer 4028, available from Henkel Corp.
(Ambler, Pa.)), and propoxylated bisphenol A diacrylate with
propoxylatlon being 2 or greater, preferably ranging from 2 to
about 30; trimethylolpropane polyacrylates with and without
alkoxylation such as ethoxylated trimethylolpropane triacrylate
with ethoxylation being 3 or greater, preferably ranging from 3 to
about 30 (e.g., Photomer 4149, Henkel Corp., and SR499, Sartomer
Company, Inc.), propoxylated trimethylolpropane triacrylate with
propoxylation being 3 or greater, preferably ranging from 3 to 30
(e.g., Photomer 4072, Henkel Corp. and SR492, Sartomer), and
ditrimethylolpropane tetraacrylate (e.g., Photomer 4355, Henkel
Corp.); alkoxylated glyceryl triacrylates such as propoxylated
glyceryl triacrylate with propoxylation being 3 or greater (e.g.,
Photomer 4096, Henkel Corp. and SR9020, Sartomer); pentaerythritol
polyacrylates with and without alkoxylation, such as
pentaerythritol tetraacrylate (e.g., SR295, available from Sartomer
Company, Inc. (West Chester, Pa.)), ethoxylated pentaerythritol
tetraacrylate (e.g., SR494, Sartomer Company, Inc.), and
dipentaerythritol pentaacrylate (e.g., Photomer 4399, Henkel Corp.,
and SR399, Sartomer Company, Inc.); isocyanurate polyacrylates
formed by reacting an appropriate functional isocyanurate with an
acrylic acid or acryloyl chloride, such as tris-(2-hydroxyethyl)
isocyanurate triacrylate (e.g., SR368, Sartomer Company, Inc.) and
tris-(2-hydroxyethyl) isocyanurate diacrylate; polyol polyacrylates
with and without alkoxylation such as tricyclodecane dimethanol
diacrylate (e.g., CD406, Sartomer Company, Inc.) and ethoxylated
polyethylene glycol diacrylate with ethoxylation being 2 or
greater, preferably ranging from about 2 to 30; hydroxy acrylates
formed by adding acrylate to bisphenol A diglycidyl ether (4 up)
and the like (e.g., Photomer 3016, Henkel Corp.); and single and
multi-ring cyclic aromatic or non-aromatic polyacrylates such as
dicyclopentadiene diacrylate and dicydopentane diacrylate.
The preparation of the inventive polymers can be carried out using
various polymerization techniques such as solution, emulsion,
microemulsion, inverse emulsion, and/or bulk polymerizations, as
well as other technologies that are available to those who are
skilled in the art. The polymerization can obviously be carried out
with or without various initiators of various concentrations. The
co- or ter-polymers can also be prepared in such a way that the
architecture of the polymers is random, block, alternating or
core-shell with or without the use of polymerization regulators
such as nitroxyl ether or other types of nitroxyl radicals.
The preferred method for making the inventive polymers is by
aqueous polymerization using a water-soluble initiator. Examples of
the suitable initiators include persulfates such as ammonium
persulfate (APS); peroxides such as hydrogen peroxide, t-butyl
hydroperoxide, and t-butyl peroxy pivalate, azo initiators such as
2,2'-azobis(2-amidinopropane) dihydrochloride,
4,4'-azobis-4-cyanovaleric acid and 2,2-azobisisobutyronitrile; and
redox initiator systems such as t-butyl hydroperoxide/Fe(II) and
ammonium persulfate/bisulfite. Aqueous solution polymerization
using ammonium persulfate (APS) is the preferred method for
preparing the polymer having the preferred cationic DADMAC
monomers. The amount of the free radical initiator used in the
polymerization process depends on total monomer concentration and
the type of monomers used and may range from about 0.2 to about
5.0% by weight of total monomer charge to achieve more than 99% of
total monomer conversion.
Hydrophobic monomer (II) dissolves, at least in part, in the
aqueous phase and copolymerizes with the preferred cationic monomer
DADMAC to form a polymer having both cationic and hydrophobic
groups. When hydrophobic monomer (II) is added to the
polymerization system in an amount higher than its water
solubility, the excess amount can form a second phase in fine
droplets if adequate agitation is provided. Without intending to
being bound to this polymerization mechanism, the droplets of
monomer (II) may serve as a monomer reservoir to provide monomer
(II) to the aqueous phase.
When a water-soluble initiator is used, copolymerization of monomer
(I) and the dissolved portion of the hydrophobic monomer (II) is
initiated in the aqueous phase. The hydrophobically modified
polymer thus formed may or may not be soluble in water depending on
hydrophobicity or water solubility and the concentration of the
monomer (II) used. The resulting polymer can possess surfactant
properties and may occur in a colloidal state giving the appearance
of translucence.
The required amount of monomer (II) may be added all at the
beginning, in increments, or added by continuous feeding to the
reactor. Continuous feeding of hydrophobic monomer (II) to the
aqueous reaction medium may have the advantage of producing
hydrophobically modified copolymers with less formation of
homopolymers or large homopolymeric segments.
It is preferred to carry out the polymerization in the absence of
oxygen. Oxygen can be removed from the reaction medium by applying
vacuum with agitation or by purging with an inert gas such as
nitrogen or argon. The polymerization can then be conducted under a
blanket of the inert gas.
The molecular weight of the polymers being prepared can range from
a thousand to millions. For example they have an average molecular
weight in the range of 1000 to 5 million Daltons. The polymers can
appear in various forms, I.e. solution, dispersion, suspension,
granules, powders, beads, blocks, etc. In the case of liquid forms
such as solution, dispersion, suspension etc., the liquid phase can
be aqueous and/or non-aqueous such as soy bean oils, esters, and
mineral oils.
Cleaning products comprise the polymeric compound of the invention
and an effective amount of one or more surfactants. Such cleaning
products may be in the form of a laundry detergent, fabric
conditioner, pre-treatment agent, after treatment agent or tumble
dry sheet having improved dye fixation and dye transfer inhibition.
They may also be in the form of a dishwashing formulation. The
inventive cleaning products comprise 0.001% to 50%, preferably 0.1
to 5% by weight of a polymeric compound of the invention.
Laundry compositions for use herein may comprise one or more
surfactants suitable for use in laundry wash and/or rinsing
products. In the most general sense, these may be chosen from one
or more of soap and non-soap anionic, cationic, nonionic,
amphoteric and zwitterionic surface-active compounds and mixtures
thereof. Many suitable surface-active compounds are available and
are fully described in the literature, for example, in
"Surface-Active Agents and Detergents", Volumes I and II, by
Schwartz, Perry and Berch.
For those compositions intended as laundry wash products,
preferably, the surfactant(s) is/are selected from one or more
soaps and synthetic non-soap anionic and non-ionic compounds.
Detergent compositions suitable for use in most automatic fabric
washing machines generally contain anionic non-soap surfactant, or
non-ionic surfactant, or combinations of the two in any suitable
ratio, optionally together with soap.
For example, laundry wash compositions of the invention may contain
linear alkylbenzene sulfonate anionic surfactants, particularly
linear alkylbenzene sulfonates having an alkyl chain length of
C.sub.8-C.sub.15. It is preferred if the level of linear
alkylbenzene sulfonate is from 0% by weight to 30% by weight, more
preferably 1% by weight to 25% by weight, most preferably from 2%
by weight to 15% by weight.
The laundry wash compositions of the invention may additionally or
alternatively contain one or more other anionic surfactants in
total amounts corresponding to percentages quoted above for alkyl
benzene sulfonates. Suitable anionic surfactants are well known to
those skilled in the art. These include primary and secondary alkyl
sulfates, particularly C.sub.8-C.sub.15 primary alkyl sulfates;
alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates;
dialkyl sulfosuccinates; and fatty acid ester sulfonates. Sodium
salts are generally preferred.
Some particular examples of such other anionic surfactants are:
alkyl ester sulfonates of the formula
R.sub.100--CH(SO.sub.3M)--COOR.sub.200, where R.sub.100 is a
C.sub.8-C.sub.20, preferably C.sub.10-C.sub.16alkyl radical,
R.sub.200 is a C.sub.1-C.sub.16, preferably C.sub.1-C.sub.3 alkyl
radical, and M is an alkaline cation (sodium, potassium, lithium),
unsubstituted or substituted ammonium (e.g. methyl, dimethyl,
trimethyl, tetramethyl ammonium, dimethyl piperidinium, etc.) or a
derivative of an alkanol amine (monoethanol amine, diethanol amine,
triethanol amine, etc.); alkyl sulfates of the formula
R.sub.300OSO.sub.3M, where R.sub.300 is a C.sub.5-C.sub.24,
preferably C.sub.10-C.sub.18 alkyl or hydroxyalkyl radical, and M
is a hydrogen atom or a cation as defined above, and their
ethyleneoxy (EO) and/or propyleneoxy (PO) derivatives, having on
average 0.5 to 30, preferably 0.5 to 10 EO and/or PO units; alkyl
amide sulfates of the formula R.sub.400CONHR.sub.500OSO.sub.3M,
where R.sub.400 is a C.sub.2-C.sub.22, preferably C.sub.6-C.sub.20
alkyl radical, R.sub.500 is a C.sub.2-C.sub.3 alkyl radical, and M
is a hydrogen atom or a cation as defined above, and their
ethyleneoxy (EO) and/or propyleneoxy (PO) derivatives, having on
average 0.5 to 60 EO and/or PO units; salts of C.sub.8-C.sub.24,
preferably C.sub.14-C.sub.20 saturated or unsaturated fatty acids,
C.sub.8-C.sub.22 primary or secondary alkyl sulfonates, alkyl
glycerol sulfonates, the sulfonated polycarboxylic acids described
in published British Patent 1,082,179, paraffin sulfonates, N-acyl,
N'-alkyl taurates, alkyl phosphates, isethionates, alkyl
succinamates, alkyl sulfosuccinates, monoesters or diesters of
sulfosuccinates, N-acyl sarcosinates, alkyl glycoside sulfates,
polyethoxycarboxylates, the cation being an alkali metal (sodium,
potassium, lithium), a substituted or non-substituted ammonium
residue (methyl, dimethyl, trimethyl, tetramethyl ammonium,
dimethyl piperidinium, etc.) or a derivative of an alkanol amine
(monoethanol amine, diethanol amine, triethanol amine, etc.); or
sophorolipids, such as those in acid or lactone form, derived from
17-hydroxyoctadecenic acid.
The laundry wash compositions of the invention may contain a
nonionic surfactant Nonionic suriactants that may be used include
the primary and secondary alcohol ethoxylates, especially the
C.sub.8-C.sub.20 aliphatic alcohols ethoxylated with an average of
from 1 to 20 moles of ethylene oxide per mole of alcohol, and more
especially the C.sub.10-C.sub.15 primary and secondary aliphatic
alcohols ethoxylated with an average of from 1 to 10 moles of
ethylene oxide per mole of alcohol. Non-ethoxylated nonionic
surfactants include alkylpolyglycosides, glycerol monoethers, and
polyhydroxyamides (glucamide).
Some particular examples of such nonionic surfactants are:
polyalkoxyienated alkyl phenols (i.e. polyethyleneoxy,
polypropyleneoxy, polybutyleneoxy), the alkyl substituent of which
has from 6 to 12 C atoms and contains from 5 to 25 alkoxylenated
units; examples are TRITON X-45, X-114, X-100 and X-102 marketed by
Rohm & Haas Co., and IGEPAL NP2 to NP17 made by Rhodia;
C.sub.8-C.sub.22 polyalkoxylenated aliphatic alcohols containing 1
to 25 alkoxylenated (ethyleneoxy, propyleneoxy) units; examples are
TERGITOL 15-S-9 and TERGITOL 24-L-6 NMW marketed by Union Carbide
Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7 and NEODOL 45-4
marketed by Shell Chemical Co., KYRO EOB marketed by The Procter
& Gamble Co., SYNPERONIC A3 to A9 made by ICI and RHODASURF IT,
DB and B made by Rhodia; the products resulting from the
condensation of ethylene oxide or propylene oxide with propylene
glycol, ethylene glycol, with a molecular weight in the order of
2000 to 10,000, such as the PLURONIC products marketed by BASF; the
products resulting from the condensation of ethylene oxide or
propylene oxide with ethylene diamine, such as the TETRONIC
products marketed by BASF; C.sub.8-C.sub.18 ethoxyl and/or propoxyl
fatty acids containing 5 to 25 ethyleneoxy and/or propyleneoxy
units; C.sub.8-C.sub.20 fatty acid amides containing 5 to 30
ethyleneoxy units; ethoxylated amines containing 5 to 30
ethyleneoxy units; alkoxylated amidoamines containing 1 to 50,
preferably 1 to 25 and in particular 2 to 20 alkyleneoxy
(preferably ethyleneoxy) units; amine oxides such as the oxides of
alkyl C.sub.10-C.sub.18 dimethylamines, the oxides of alkoxy
C.sub.8-C.sub.22 ethyl dihydroxyethylamines; alkoxylated terpene
hydrocarbons such as ethoxylated and/or propoxylated- or -pinenes,
containing 1 to 30 ethyleneoxy and/or propyleneoxy units;
alkylpolyglycosides obtainable by condensation (for example by acid
catalysis) of glucose with primary fatty alcohols (e.g. U.S. Pat.
No. 3,598,865; U.S. Pat. No. 4,565,647; EP-A-132 043; EP-A-132 046)
having a C.sub.4-C.sub.20, preferably C.sub.8-C.sub.18 alkyl group
and an average number of glucose units in the order of 0.5 to 3,
preferably in the order of 1.1 to 1.8 per mole of
alkylpolyglycoside (APG), particularly those having a
C.sub.8-C.sub.14 alkyl group and on average 1.4 glucose units per
mole a C.sub.12-C.sub.14 alkyl group and on average 1.4 glucose
units per mole a C.sub.8-C.sub.14 alkyl group and on average 1.5
glucose units per mole a C.sub.8-C.sub.10 alkyl group and on
average 1.6 glucose units per mole marketed under the names
GLUCOPON 600 EC, GLUCOPON 600 CSUP, GLUCOPON 650 EC and GLUCOPON
225 CSUP respectively and made by HENKEL.
The level of total nonionic surfactant is from 0% by weight to 30%
by weight, preferably from 1% by weight to 25% by weight, more
preferably from 2% by weight to 15% by weight.
Another class of suitable surfactants comprises certain mono-long
chain-alkyl cationic surfactants for use in main-wash laundry
compositions according to the invention. Cationic suriactants of
this type include quaternary ammonium salts of the general formula
R.sub.10R.sub.20R.sub.30R.sub.40N.sup.+ X.sup.- wherein the R
groups are long or short hydrocarbon chains, typically alkyl,
hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion
(for example, compounds in which R.sub.10 is a C.sub.8-C.sub.22
alkyl group, preferably a C.sub.8-C.sub.10 or C.sub.12-C.sub.14
alkyl group, R.sub.20 is a methyl group, and R.sub.30 and R.sub.40,
which may be the same or different, are methyl or hydroxyethyl
groups); and cationic esters (for example, choline esters).
The choice of surface-active compound (surfactant), and the amount
present in the laundry wash compositions according to the
invention, will depend on the intended use of the detergent
composition. In fabric washing compositions, different surfactant
systems may be chosen, as is well known to the skilled formulator,
for hand washing products and for products intended for use in
different types of washing machines. The total amount of surfactant
present will also depend on the intended end use and may be as high
as 60% by weight, for example, in a composition for washing fabrics
by hand. In compositions for machine-washing of fabrics, an amount
of from 5 to 40% by weight is generally appropriate. Typically the
compositions will comprise at least 2% by weight surfactant e.g.
2-60%, preferably 15-40% and most preferably 25-35%.
In the case of laundry rinse compositions according to the
invention the surfactant(s) is/are preferably selected from fabric
conditioning agents. In fact, conventional fabric conditioning
agents may be used. These conditioning agents may be cationic or
non-ionic. If the fabric conditioning compound is to be employed in
a main wash detergent composition the compound will typically be
non-ionic. If used in the rinse phase, they will typically be
cationic. They may for example be used in amounts from 0.5% to 35%,
preferably from 1% to 30% more preferably from 3% to 25% by weight
of the composition.
Preferably the fabric conditioning agent(s) have two long chain
alkyl or alkenyl chains each having an average chain length greater
than or equal to C.sub.16. Most preferably at least 50% of the long
chain alkyl or alkenyl groups have a chain length of C.sub.8 or
above. It is preferred that the long chain alkyl or alkenyl groups
of the fabric conditioning agents are predominantly linear.
The fabric conditioning agents are preferably compounds that
provide excellent softening, and are characterized by a chain
melting L to L transition temperature greater than 25.degree. C.,
preferably greater than 35.degree. C., most preferably greater than
45.degree. C.
Substantially insoluble fabric conditioning compounds in the
context of this invention are defined as fabric conditioning
compounds having a solubility less than 1.times.10.sup.-3% by
weight in demineralized water at 20.degree. C. Preferably the
fabric softening compounds have a solubility less than
1.times.10.sup.-4 wt %, most preferably less than 1.times.10.sup.-8
to 1.times.10.sup.-8. Preferred cationic fabric softening agents
comprise a substantially water-insoluble quaternary ammonium
material comprising a single alkyl or alkenyl long chain having an
average chain length greater than or equal to C.sub.20 or, more
preferably, a compound comprising a polar head group and two alkyl
or alkenyl chains having an average chain length greater than or
equal to C.sub.14.
Preferably, the catatonic fabric softening agent is a quaternary
ammonium material or a quaternary ammonium material containing at
least one ester group. The quaternary ammonium compounds containing
at least one ester group are referred to herein as ester-linked
quaternary ammonium compounds.
As used in the context of the quaternary ammonium cationic fabric
softening agents, the term ester group, includes an ester group
which is a linking group in the molecule.
It is preferred for the ester-linked quaternary ammonium compounds
to contain two or more ester groups. In both monoester and the
diester quaternary ammonium compounds it is preferred if the ester
group(s) is a linking group between the nitrogen atom and an alkyl
group. The ester groups(s) are preferably attached to the nitrogen
atom via another hydrocarbyl group.
Also preferred are quaternary ammonium compounds containing at
least one ester group, preferably two, wherein at least one higher
molecular weight group containing at least one ester group and two
or three lower molecular weight groups are linked to a common
nitrogen atom to produce a cation and wherein the electrically
balancing anion is a halide, acetate or lower alkosulfate ion, such
as chloride or methosulfate. The higher molecular weight
substituent on the nitrogen is preferably a higher alkyl group,
containing 12 to 28, preferably 12 to 22, e.g. 12 to 20 carbon
atoms, such as coco-allkyl, tallowalkyl, hydrogenated tallowalkyl
or substituted higher alkyl, and the lower molecular weight
substituents are preferably lower alkyl of 1 to 4 carbon atoms,
such as methyl or ethyl, or substituted lower alkyl. One or more of
the said lower molecular weight substituents may include an aryl
moiety or may be replaced by an aryl, such as benzyl, phenyl or
other suitable substituents.
Preferably the quaternary ammonium material is a compound having
two C.sub.12-C.sub.22 alkyl or alkenyl groups connected to a
quaternary ammonium head group via at least one ester link,
preferably two ester links or a compound comprising a single long
chain with an average chain length equal to or greater than
C.sub.20.
More preferably, the quaternary ammonium material comprises a
compound having two long chain alkyl or alkenyl chains with an
average chain length equal to or greater than C.sub.14. Even more
preferably each chain has an average chain length equal to or
greater than C.sub.16. Most preferably at least 50% of each long
chain alkyl or alkenyl group has a chain length of C.sub.18. It is
preferred If the long chain alkyl or alkenyl groups are
predominantly linear.
The most preferred type of ester-linked quaternary ammonium
material that can be used in laundry rinse compositions according
to the invention is represented by the formula (A):
##STR00007## wherein T is
##STR00008## each R.sup.50 group is independently selected from
C.sub.1-4 alkyl, hydroxyalkyl or C.sub.2-4alkenyl groups; and
wherein each R.sup.51 group is independently selected from
C.sub.8-28 alkyl or alkenyl groups; Y.sup.- is any suitable
counter-ion, i.e. a halide, acetate or lower alkosulfate ion, such
as chloride or methosulfate; w is an integer from 1-5 or is 0; and
y is an integer from 1-5.
It is especially preferred that each R.sup.50 group is methyl and w
is 1 or 2.
It is advantageous for environmental reasons if the quaternary
ammonium material is biologically degradable. Preferred materials
of this class such as 1,2 bis[hardened
tallowoyloxy]-3-trimethylammonium propane chloride and their method
of preparation are, for example, described in U.S. Pat. No.
4,137,180. Preferably these materials comprise small amounts of the
corresponding monoester as described in U.S. Pat. No. 4,137,180 for
example 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium
propane chloride.
Another class of preferred ester-linked quaternary ammonium
materials for use in laundry rinse compositions according to the
invention can be represented by the formula (B):
##STR00009## wherein T is
##STR00010## R.sup.50, R.sup.51, and Y.sup.- are as defined
above.
Of the compounds of formula (B), di-(tallowyloxyethyl)-dimethyl
ammonium chloride, available from Hoechst, is the most preferred.
Di-(hardened tallowyloxyethyl)dimethyl ammonium chloride, ex
Hoechst and di-(tallowyloxyethyl)-methyl hydroxyethyl methosulfate
are also preferred.
Another preferred class of quaternary ammonium cationic fabric
softening agent is defined by formula (C):
##STR00011## where R.sup.50, R.sup.51 and Y.sup.- are as
hereinbefore defined.
A preferred material of formula (C) is di-hardened tallow-diethyl
ammonium chloride, sold under the Trademark ARQUAD 2HT.
The optionally ester-linked quaternary ammonium material may
contain optional additional components, as known in the art, in
particular, low molecular weight solvents, for instance isopropanol
and/or ethanol, and co-actives such as nonionic softeners, for
example fatty acid or sorbitan esters.
Detergency Builders
The compositions of the invention, when used as laundry wash
compositions, will generally also contain one or more detergency
builders. The total amount of detergency builder in the
compositions will typically range from 5 to 80% by weight,
preferably from 10 to 60% by weight.
Inorganic builders that may be present include sodium carbonate, if
desired in combination with a crystallization seed for calcium
carbonate, as disclosed in GB 1 437 950 (Unilever); crystalline and
amorphous aluminosilicates, for example, zeolites as disposed in GB
1 473 201 (Henkel), amorphous aluminosilicates as disclosed in GB 1
473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates
as disclosed in GB 1 470 250 (Procter & Gamble); and layered
silicates as disclosed in EP 164 514B (Hoechst). Inorganic
phosphate builders, for example, sodium orthophosphate,
pyrophosphate and tripolyphosphate are also suitable for use with
this invention.
The compositions of the invention preferably contain an alkali
metal, preferably sodium, aluminosilicate builder. Sodium
aluminosillcates may generally be incorporated in amounts of from
10 to 70% by weight (anhydrous basis), preferably from 25 to 50% by
weight.
The alkali metal aluminosilicate may be either crystalline or
amorphous or mixtures thereof, having the general formula: 0.8-1.5
Na.sub.2O. Al.sub.2O.sub.3. 0.8-6 SiO.sub.2.
These materials contain some bound water and are required to have a
calcium ion exchange capacity of at least 50 mg CaO/g. The
preferred sodium aluminosilicates contain 1.5-3.5 SiO.sub.2 units
(in the formula above). Both the amorphous and the crystalline
materials can be prepared readily by reaction between sodium
silicate and sodium aluminate, as amply described in the
literature. Suitable crystalline sodium aluminosilicate
ion-exchange detergency builders are described, for example, in GB
1 429 143 (Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known commercially
available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely
used in laundry detergent powders. However, according to a
preferred embodiment of the invention, the zeolite builder
incorporated in the compositions of the invention is maximum
aluminum zeolite P (zeolite MAP) as described and claimed in EP 384
070A (Unilever). Zeolite MAP is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to aluminum
ratio not exceeding 1.33, preferably within the range of from 0.90
to 1.33, and more preferably within the range of from 0.90 to
1.20.
Especially preferred is zeolite MAP having a silicon to aluminum
ratio not exceeding 1.07, more preferably about 1.00. The calcium
binding capacity of zeolite MAP is generally at least 150 mg CaO
per g of anhydrous material.
Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers, and
acrylic phosphinates; monomeric polycarboxylates such as citrates,
gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates,
carboxymethyloxy succinates, carboxymethyloxymalonates,
dipicolinates, hydroxyethyliminodiacetates, alkyl- and
alkenylmalonates and succinates; and sulfonated fatty add salts.
This list is not intended to be exhaustive. Especially preferred
organic builders are citrates, suitably used in amounts of from 5
to 30% by weight, preferably from 10 to 25% by weight; and acrylic
polymers, more especially acrylic/maleic copolymers, suitably used
in amounts of from 0.5 to 15% by weight, preferably from 1 to 10%
by weight.
Builders, both inorganic and organic, are preferably present in
alkali metal salt, especially sodium salt, form.
Laundry wash compositions according to the invention may also
suitably contain a bleach system. Fabric washing compositions may
desirably contain peroxy bleach compounds, for example, inorganic
persalts or organic peroxyacids, capable of yielding hydrogen
peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides such as
urea peroxide, and inorganic persalts such as the alkali metal
perborates, percarbonates, perphosphates, persilicates and
persulfates. Preferred inorganic persalts are sodium perborate
monohydrate and tetrahydrate, and sodium percarbonate.
Especially preferred is sodium percarbonate having a protective
coating against destabilization by moisture. Sodium percarbonate
having a protective coating comprising sodium metaborate and sodium
silicate is disclosed in GB 2 123 044B (Kao).
The peroxy bleach compound is suitably present in an amount of from
0.1 to 35% by weight, preferably from 0.5 to 25% by weight. The
peroxy bleach compound may be used in conjunction with a bleach
activator (bleach precursor) to improve bleaching action at low
wash temperatures. The bleach precursor is suitably present in an
amount of from 0.1 to 8% by weight, preferably from 0.5 to 5% by
weight.
Preferred bleach precursors are peroxycarboxylic acid precursors,
more especially peracetic acid precursors and pemonanoic acid
precursors. Especially preferred bleach precursors suitable for use
in the present invention are N,N,N',N',-tetracetyl ethylenediamine
(TAED) and sodium nonanoyloxybenzene sulfonate (SNOBS). The novel
quaternary ammonium and phosphonium bleach precursors disclosed in
U.S. Pat. No. 4,751,051 and U.S. Pat No. 4,818,426 (Lever Brothers
Company) and EP 402 971A (Unilever), and the cationic bleach
precursors disposed in EP 284 292A and EP 303 520A (Kao) are also
of interest.
The bleach system can be either supplemented with or replaced by a
peroxyacid. Examples of such peracids can be found in U.S. Pat. No.
4,686,063 and U.S. Pat. No. 5,397,501 (Unilever). A preferred
example is the imido peroxycarboxylic class of peracids described
in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289. A
particularly preferred example is phthalimido peroxycaproic acid
(PAP). Such peracids are suitably present at 0.1-12%, preferably
0.5-10%.
A bleach stabilizer (transition metal sequesterant) may also be
present. Suitable bleach stabilizers include ethylenediamine
tetra-acetate (EDTA), the polyphosphonates such as DEQUEST.TM. and
non-phosphate stabilizers such as EDDS (ethylenediamine di-succinic
add). These bleach stabilizers are also useful for stain removal
especially in products containing low levels of bleaching species
or no bleaching species.
An especially preferred bleach system comprises a peroxy bleach
compound (preferably sodium percarbonate optionally together with a
bleach activator), and a transition metal bleach catalyst as
described in EP 458 397A, EP 458 398A and EP 509 787A
(Unilever).
Laundry wash compositions according to the invention may also
contain one or more enzyme(s). Suitable enzymes include the
proteases, amylases, cellulases, oxidases, peroxidases and lipases
usable for incorporation in detergent compositions. Preferred
proteolytic enzymes (proteases) are catalytically active protein
materials which degrade or alter protein types of stains in a
hydrolyses reaction when present as in fabric stains. They may be
of any suitable origin, such as vegetable, animal, bacterial or
yeast origin.
Proteolytic enzymes or proteases of various qualities and origins
and having activity in various pH ranges of from 4-12 are available
and can be used in the instant invention. Examples of suitable
proteolytic enzymes are the subtilisins which are obtained from
particular strains of B. Subtilwas B. licheniformis, such as the
commercially available subtilisins MAXATASE.TM., as supplied by
Gist Brocades N. V., Delft, Holland, and ALCALASE.TM., as supplied
by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of
Bacillus having maximum activity throughout the pH range of 8-12,
being commercially available, e.g. from Novo industri A/S under the
registered trade-names ESPERASE.TM. and SAVINASE.TM.. The
preparation of these and analogous enzymes is described in GB 1 243
785. Other commercial proteases are KAZUSASE.TM., obtainable from
Showa-Denko of Japan), OPTIMASE.TM., from Miles Kali-Chemie,
Hannover, West Germany), and SUPERASE.TM., obtainable from Pfizer
of U.S.A).
Detergency enzymes are commonly employed in granular form in
amounts of from about 0.1 to about 3.0% by weight However, any
suitable physical form of enzyme may be used.
The compositions of the invention may contain other optional
ingredients such as alkali metal, preferably sodium carbonate, in
order to increase detergency and ease processing. Sodium carbonate
may suitably be present in amounts ranging from 1 to 60% by weight,
preferably from 2 to 40% by weight However, compositions containing
little or no sodium carbonate are also within the scope of the
invention.
Powder flow may be improved by the incorporation of a small amount
of a powder structurant, for example, a fatty add (or fatty acid
soap), a sugar, an acrylate or acrylate/maleate copolymer, or
sodium silicate. One preferred powder structurant is fatty add
soap, suitably present in an amount of from 1 to 5% by weight.
Yet other materials that may be present in detergent compositions
of the invention include sodium silicate; anti-redeposition agents
such as cellulosic polymers; inorganic salts such as sodium
sulfate; lather control agents or lather boosters as appropriate;
proteolytic and lipolyfic enzymes; dyes; colored speckles;
perfumes; foam controllers; fluorescent whiteners and decoupling
polymers. This list is not intended to be exhaustive.
Still other materials that may be present in detergent compositions
of the invention include other additives such as softeners,
perfumes, soil release polymers, colorants, preservatives,
antimicrobials with various activities against various
microorganisms, insect repellents, dust mites repellents and/or
otherwise controlling agents, optical brighteners, UV absorbers,
other light management agents, ionization agents, antifoam agents,
enzymes of various kinds, bleaching agents, oxidation catalysts,
zeolites and odor suppressing agents including but not limited to
cydodextrin and its various derivatives.
The inventive composition, when diluted in the wash liquor (during
a typical wash cycle), will typically give a pH of the wash liquor
from 7 to 11, preferably from 7 to 10.5, for a wash product.
Treatment of a fabric with a polymer having both cationic and
hydrophobic groups in accordance with an aspect of the present
invention can be made by any suitable method such as washing,
soaking or rinsing.
Typically the treatment will involve a washing or rinsing method
such as treatment in the main wash or rinse cycle of a washing
machine and involves contacting the fabric with an aqueous medium
comprising the composition according to the first aspect of the
present invention.
Compositions according to another aspect of the present invention
may be formulated in any convenient form, for example as powders,
liquids (aqueous or non-aqueous) or tablets.
Particulate detergent compositions are suitably prepared by
spray-drying a slurry of compatible heat-insensitive ingredients,
and then spraying on or post-dosing those ingredients unsuitable
for processing via the slurry. The skilled detergent formulator
will have no difficulty in deciding which ingredients should be
included in the slurry and which should not.
Particulate detergent compositions of the invention preferably have
a bulk density of at least 400 g/l, more preferably at least 500
g/l. Especially preferred compositions have bulk densities of at
least 650 g/liter, more preferably at least 700 g/liter.
Such powders may be prepared either by post-tower densification of
spray-dried powder, or by wholly non-tower methods such as dry
mixing and granulation; in both cases a high-speed mixer/granulator
may advantageously be used. Processes using high-speed
mixer/granulators are disclosed, for example, in EP 340 013A, EP
367 339A, EP 390 251A and EP 420 317A (Unilever).
Liquid detergent compositions can be prepared by admixing the
essential and optional ingredients thereof in any desired order to
provide compositions containing components in the requisite
concentrations. Liquid compositions according to the present
invention can also be in compact form, which means it will contain
a lower, level of water compared to a conventional liquid
detergent.
The following examples describe certain embodiments of this
invention, but the invention is not limited thereto. It should be
understood that numerous changes to the disclosed embodiments can
be made in accordance with the disclosure herein without departing
from the spirit or scope of the invention. These examples are
therefore not meant to limit the scope of the invention. Rather,
the scope of the invention is to be determined only by the appended
claims and their equivalents. In these examples all parts given are
by weight unless otherwise indicated.
EXAMPLE 1
A 1-liter reactor equipped with a condenser, a thermometer, a
nitrogen inlet, and an overhead agitator is charged with 453.8 g of
66% monomer DADMAC in water, 15.8 g of methyl methacrylate (MMA),
57.4.0 g of deionized water and 0.15 g of 20% Na.sub.4EDTA
solution. The polymerization mixture is purged with nitrogen and
heated with agitation to a temperature of 90.degree. C. An aqueous
solution containing 5.1 g of ammonium persulfate (APS) is slowly
fed to the reactor over 190 minutes. The reaction temperature is
allowed to increase to above 100.degree. C. and then maintained at
reflux temperature (100 to 110.degree. C.) during the APS feed
period. After the APS feed, the reaction temperature is lowered
down to and held at 95.degree. C. for about 30 minutes. Then an
aqueous solution containing 5.6 g of sodium metabisulfite (MBS) is
added over 30 minutes. The reactor content is held at 95.degree. C.
for another 30 minutes to complete the polymerization (above 99%
conversion). The polymer solution is diluted with sufficient water
to about 35% solids and cooled to room temperature. Total monomer
conversion is measured to be above 99.5%. The final product has a
Brookfield viscosity of 23,400 cps at 25.degree. C. and 33.7%
polymer solids.
EXAMPLE 2
A 1-liter reactor equipped with a condenser, a thermometer, a
nitrogen inlet, and an overhead agitator is charged with 453.8 g of
66% monomer DADMAC in water, 15.8 g of ethoxylated nonylphenol
acrylate (ENPA)), 57.4.0 g of deionized water and 0.15 g of 20%
Na.sub.4EDTA solution. The polymerization mixture is purged with
nitrogen and heated with agitation to a temperature of 90.degree.
C. An aqueous solution containing 5.1 g of ammonium persulfate
(APS) is slowly fed to the reactor over 190 minutes. The reaction
temperature is allowed to increase to above 100.degree. C. and then
maintained at reflux temperature (100 to 110.degree. C.) during the
APS feed period. After the APS feed, the reaction temperature is
lowered down to and held at 95.degree. C. for about 30 minutes.
Then an aqueous solution containing 5.6 g of sodium metabisulfite
(MBS) is added over 30 minutes. The reactor content is held at
95.degree. C. for another 30 minutes to complete the polymerization
(above 99% conversion). The polymer solution is diluted with
sufficient water to about 35% solids and cooled to room
temperature. Total monomer conversion is measured to be above
99.5%. The final product has a Brookfield viscosity of 15,700 cps
at 25.degree. C. and 33.7% polymer solids.
EXAMPLE 3
This example demonstrates addition of hydrophobic monomer II by
feeding. The polymerization procedure is the same as example 1
except that the amount of 15.8 9 methyl methacrylate is fed to the
reactor over about 45 minutes when the APS initiator feed is
started. The polymer solution is diluted with sufficient water to
about 35% solids and cooled to room temperature. Total monomer
conversion is measured to be above 99.5%. The final product has a
Brookfield viscosity of 19,500 cps at 25.degree. C. and 35% polymer
solids. The final polymer product is dear as compared to the
emulsion appearance of the Example 1 product.
EXAMPLE 4
Application: Fix Before Wash I
Fixation:
The product is applied from an aqueous solution to a dyed fabric
sheet ("Bleeder") and spin-dried.
Wash:
This treated fabric is washed together with a colorless Fabric
("Acceptor") using a standard detergent without any dye fixing or
dye transfer-inhibiting agent. The fabrics are spin-dried, rinsed
with dear water, spin-dried and dried at 60.degree. C. In every
subsequent wash cycle the "Acceptor" is replaced by a new one.
Performance is assessed by the absorption (extinction at absorption
maximum) of the Fix liquor, wash liquor and the dye deposition on
the white "Acceptor" fabric (Delta E).
The resulting absorption and Delta E values are used to calculate
the corresponding amount of dyestuff. All results are given on the
amount of dyestuff lost from one kg of dyed fabric.
Application Conditions:
5 g of a dyed cotton fabric (2.09% Direct Blue 78) are treated 15
minutes with 2.5 g/l or 5 g/l of a solution containing 1% active
matter of the polymer at a Liquor Ratio of 1:10 at 40.degree. C.
The fabric is removed from the liquor, spin dried and washed for 15
minutes together with 5 g of a colorless cotton fabric "Acceptor"
in a 2.5 g/l ECE77 detergent solution a Liquor Ratio of 1:10 at
40.degree. C. The fabrics are squeezed, rinsed under running tap
water, spin-dried and dried in an oven at 60.degree. C.
This procedure is repeated 2 times with the same "Bleeder" using a
new "Acceptor" in every wash.
Results:
[mg dye lost per kg of dyed fabric]
TABLE-US-00001 2.5 g/l dosage 5.0 g/l dosage Lost into Liquor onto
Lost into Liquor onto Product FIX WASH FABRIC total FIX WASH FABRIC
total None 1320 620 1300 3240 1320 620 1300 3240 Ex. 2 223 695 1549
2466 7 410 1004 1420 TINOFIX CL 749 503 824 2075 163 454 607 1224
Example 1 172 644 1403 2219 9 309 729 1046
Where Ex. 2 is a copolymer of DADMAC and acrylamide and TINOFIX CL
is a commercial product from Ciba Specialty Chemicals.
The results shown above indicate that the amount of dyes lost to
the fix liquor, wash liquor and to the acceptor fabrics is much
reduced when small amount of hydrophobically modified DADMAC
polymer is used to treat the fabrics before washing; hence there is
excellent performance in preventing dyes from bleeding.
EXAMPLE 5
Application: Fix During Wash
A colored fabric ("Bleeder") is washed together with a colorless
Fabric ("Acceptor") using a standard detergent without any dye
fixing or dye transfer-inhibiting agent. The dye-fixing polymer is
added to the wash liquor just before the application. The fabrics
are spin-dried, rinsed with clear water, spin dried and dried at
60.degree. C. In every following wash cycle the "Acceptor" is
substituted by a new one.
Performance is assessed by the absorption (extinction at absorption
maximum) of the Wash liquor and the dye deposition on the white
"Acceptor" fabric (Delta E).
The resulting absorption and Delta E values are used to calculate
the corresponding amount of dyestuff. All results are given on the
amount of dyestuff lost from one kg of dyed fabric.
Application Conditions:
5g of a dyed cotton fabric (2.09% Direct Blue 78) and 5 g of a
colorless cotton fabric "Acceptor" in a 2.5 g/l standard detergent
ECE77 solution. The dye-fixing polymer is added to the detergent
solution at 1% on weight of detergent just before application. The
Liquor Ratio is 1:10 and the washing temperature is 40.degree.
C.
The fabrics are squeezed, rinsed under running tap water,
spin-dried and dried in an oven at 60.degree. C.
This procedure is repeated 2 times with the same "Bleeder" using a
new "Acceptor" in every wash.
Results:
[mg dye lost per kg of dyed fabric]
TABLE-US-00002 Lost Dyestuff Into Product Liquor onto Fabric Total
TINOFIX CL 878 943 1821 SOKALAN HP 56 2075 434 2509 PVP K-30 1707
690 2397 none 745 1569 2314 Example 1 565 710 1275 Example 2 496
640 1136
Where SOKALAN HP 56 and PVP K-30 are both commercially available
poly(vinylpyrrolidone)-based anti-redeposition agents.
Results as shown above indicate that when hydrophobically modified
DADMAC polymers are added in small amounts to a laundry detergent,
the amount of the dyes lost to the liquor is very much reduced. In
addition, such polymers also help prevent the migrating dyes from
redepositing in a way that is similar to the commercially available
anti-deposition agents such as SOKALAN HP 56 and PVP K-30.
EXAMPLE 6
Preparation of Hydrophobically Modified Polymers by Co-polymerizing
DADMAC with Various Hydrophobic Monomers
Hydrophobically modified polymers were prepared by copolymerizing
DADMAC with various amounts, i.e. 2.5%, 5% and 10% (w/w), of methyl
methacrylate, butyl methacrylate, benzyl methacrylate, using the
procedure as described in Example 1.
TABLE-US-00003 Total Brookfield monomer viscosity Polymer
conversion Solids (25.degree. C.) Comparison (1) DADMAC 99.9% 35%
7,850 Ex. (100%) Example 6A (2) DADMAC:MMA >99% 35% 23,600
(97.5:2.5) Example 6B (3) DADMAC:Methyl >99% 32% 9,000 MA (95:5)
Example 6C DADMAC:Butyl >99% 35% 15,200 MA (95:5) Example 6D
DADMAC:Benzyl >99% 35% 15,400 MA (95:5)
Application tests as described below were carried out to study the
influence of the type of the hydrophobic monomers and/or the amount
of hydrophobic monomer on the color fixation performance. It is
noted that the examples are for Illustration purposes only and the
selection and usage of the hydrophobic monomers are by no means
restricted by these examples.
EXAMPLE 7
Application: Fix Before Wash Tests with Hydrophobically Modified
Polymers Prepared by Polymerizing DADMAC and Various Amount of
Methyl Methacrylate Monomer
The application conditions for this set of tests were modified
slightly in comparison with what was described in Example 4. Thus,
5g Bleeder fabrics made of 100% cotton and dyed with 2.09% Direct
Blue and/or 3.0% Direct Red 227 respectively were rinsed in an
aqueous solution containing 5 g/l of a 1% solution of the polymer
being tested. The rinsing was carried out at 25.degree. C. for 30
minutes, at a 10:1 liquor ratio and water hardness 11.degree. dH.
The drying was carried out at room temperature
This pre fixed Bleeder is washed together with: 5g
Acceptor--bleached 100% cotton fabric 2.5 g/l ECE 77 standard
detergent Liquor ratio 10:1, water hardness 11.degree. dH
30.degree. C., 15 Minutes.
The amount of lost dye is calculated from the absorption of the
wash liquor and the Delta E value of the Acceptor.
The following results were obtained with Cotton dyed with D Blue
078 dye (results expressed as mg dyes lost per kg of dyed
fabrics)
TABLE-US-00004 Lost dyes To To Polymer Monomer composition acceptor
liquor Total Comparison (4) DADMAC 280 161 414 example Example 6A
DADMAC:MMA (97.5:2.5) 203 119 322 Example 6B DADMAC:MMA (95:5) 212
121 333 No polymer 472 258 739
Results obtained with Cotton dyed with D Red 227 dye (results
expressed as mg dyes lost per kg of dyed fabrics)
TABLE-US-00005 Lost dyes To To Polymer Monomer composition acceptor
liquor Total comparison (5) DADMAC 157 165 322 example Example 6A
DADMAC:MMA (97.5:2.5) 134 135 269 Example 6B DADMAC:MMA (95:5) 137
150 287 No polymer 254 203 458
The results showed that the hydrophobically modified polymers were
able to afford significant improvement in dye fixation performances
and the degree of improvement was dependent on the amount of the
hydrophobic monomers in the copolymers.
EXAMPLE 8
Application: Fix Before Wash Tests with Hydrophobically Modified
Polymers Prepared by Polymerizing 95% of DADMAC and 5% of Various
Hydrophobic Monomers
With exception of the polymers used in the tests, all other test
conditions were the same as described in Example 7.
Results obtained with Cotton dyed with D Blue 078 dyes (results
expressed as mg dyes lost per kg of dyed fabrics)
TABLE-US-00006 Lost dyes To To Polymer Monomer composition acceptor
liquor Total Comparison (6) DADMAC 280 161 414 Example (100%)
Example 6B (7) DADMAC:Methyl 212 121 333 MA (95:5) Example 6C
DADMAC:Butyl MA (95:5) 212 141 353 Example 6D DADMAC:Benzyl MA
(95:5) 212 127 339 No polymer 472 258 739
Results obtained with Cotton dyed with D Red 227 dye (results
expressed as mg dyes lost per kg of dyed fabrics)
TABLE-US-00007 Lost dyes To To Polymer Monomer composition acceptor
liquor Total Comparison (8) DADMAC (100%) 157 165 322 Example
Example 6B DADMAC:Methyl MA 136 145 281 (95:5) Example 6C
DADMAC:Butyl MA (95:5) 130 143 273 Example 6D DADMAC:Benzyl MA 120
131 251 (95:5) No polymer 254 203 458
The results showed that the hydrophobically modified polymers were
able to afford significant improvement in dye fixation performances
and the degree of improvement was dependent on the type of the
hydrophobic monomers used in the copolymers.
* * * * *